title: Stepwise effects of the BCR sequential chemical extraction procedure on dissolution and metal release from common ferromagnesian clay minerals: a combined solution chemistry and X-ray powder diffraction study.
abstract: Sequential extraction procedures (SEPs) are commonly used to determine speciation of trace metals in soils and sediments. However, the non-selectivity of reagents for targeted phases has remained a lingering concern. Furthermore, potentially reactive phases such as phyllosilicate clay minerals often contain trace metals in structural sites, and their reactivity has not been quantified. Accordingly, the objective of this study is to analyze the behavior of trace metal-bearing clay minerals exposed to the revised BCR 3-step plus aqua regia SEP. Mineral quantification based on stoichiometric analysis and quantitative powder X-ray diffraction (XRD) documents progressive dissolution of chlorite (CCa-2 ripidolite) and two varieties of smectite (SapCa-2 saponite and SWa-1 nontronite) during steps 1-3 of the BCR procedure. In total, 8 (+/-1) % of ripidolite, 19 (+/-1) % of saponite, and 19 (+/-3) % of nontronite (% mineral mass) dissolved during extractions assumed by many researchers to release trace metals from exchange sites, carbonates, hydroxides, sulfides and organic matter. For all three reference clays, release of Ni into solution is correlated with clay dissolution. Hydrolysis of relatively weak Mg-O bonds (362 kJ/mol) during all stages, reduction of Fe(III) during hydroxylamine hydrochloride extraction and oxidation of Fe(II) during hydrogen peroxide extraction are the main reasons for clay mineral dissolution. These findings underscore the need for precise mineral quantification when using SEPs to understand the origin/partitioning of trace metals with solid phases.
authors.affiliation: Geology Department, Middlebury College, Middlebury, Vermont 05753 USA. pryan@middlebury.edu
authors.forename: P C
authors.initials: PC
authors.lastname: Ryan
authors.forename: S
authors.initials: S
authors.lastname: Hillier
authors.forename: A J
authors.initials: AJ
authors.lastname: Wall
mesh_terms: D000538:Aluminum Silicates / Q000737:chemistry*; D002623:Chemistry Techniques, Analytical / Q000379:methods*; D002712:Chlorides / Q000737:chemistry; D000077215:Clay; D007501:Iron / Q000032:analysis*; D008274:Magnesium / Q000032:analysis*; D008670:Metals / Q000032:analysis; D017640:Silicates / Q000737:chemistry; D012996:Solutions; D014131:Trace Elements / Q000032:analysis; D014961:X-Ray Diffraction
chemical_list: D000538:Aluminum Silicates; D002712:Chlorides; D008670:Metals; D017640:Silicates; D012996:Solutions; D014131:Trace Elements; C033214:Smectite; D007501:Iron; D008274:Magnesium; D000077215:Clay; C001599:chlorite